This invention relates to beta-alkylidene phenethyl alcohol esters and ethers of our invention defined according to the generic structure: ##STR3## wherein R.sub.5 represents hydrogen or methyl; wherein R.sub.6 represents one of the moieties: ##STR4## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents the same or different hydrogen or methyl; wherein R.sub.7 represents methyl or ethyl; and wherein R.sub.8 represents hydrogen or methyl; and uses thereof in augmenting or enhancing the aroma of perfume compositions or perfumed articles including perfumed polymers.
Materials which can provide rose, cinnamon, carnation, lilac, spicy, ozoney and green aromas with spicy, clove, lilac, piney, anisic and fruity topnotes particularly those materials which are relatively inexpensive are highly sought after in the art of perfumery. Many of the natural materials which provide such fragrance profiles and contribute such desired nuances to perfumery compositions and perfumed articles are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is, accordingly, a continuing effort to find synthetic materials which will replace the essential fragrance notes produced by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the composition. The search for more materials which can provide a more refined rose, cinnamon, carnation, lilac, spicy, ozoney and green aroma profile and spicy, clove, lilac, piney, anisic and fruity topnotes has been difficult and relatively costly in the area of both natural products and synthetic products.
Aryl alkanols are known as perfumery materials particularly the well known phenylethyl alcohol which provides rose, cinnamon and honey aromas to floral fragrance formulations and perfumed articles.
Beta-methylene phenethyl acetate having the structure: ##STR5## is disclosed to provide sweet, lilac, hyacinth and ripe grain aromas to perfumed articles and perfume formulations in Canadian Letters Pat. No. 1,157,036 issued on Nov. 15, 1983 as well as European Pat. No. 035,183 published on Feb. 20, 1981. The said European and Canadian Patents also disclose other esters of methylene phenethyl alcohol useful in perfumery but do not disclose carbonate esters, ethers or borate esters and furthermore do not disclose the alcohol itself to be so useful.
Indeed, the alkylidene phenethyl alcohols of our invention have unexpected, unobvious and advantageous intense aromas and give rise to unexpected, unobvious and advantageous properties with respect to perfume compositions, perfumed articles and perfumed polymers.
The use of the borate esters in perfumery is indeed disclosed in U.S. Pat. No. 3,239,421 issued on Mar. 8, 1966 (entitled "Perfume Composition Containing 2-(beta-phenylethoxy)-4,4,6-trimethyl-1,3-dioxa-2-borinane) the specification for which is incorporated by reference herein.
Furthermore, the use of boric acid esters as intermediates in the synthesis of chemicals useful in augmenting or enhancing the aroma of perfumes and perfume compositions is also disclosed in the prior art.
Thus, the borate ester of 3-endo-methyl-3-exo(4'-methyl-5'-hydroxypentyl)norcamphor is shown as an intermediate for producing dihydro-beta-santalol in U.S. Pat. No. 3,662,007 issued on May 9, 1972.
However, arylalkanol esters of boric acid and glycol borates are shown to be useful for killing bacteria and fungi in U.S. Pat. No. 3,564,091 issued on Feb. 16, 1971. Indeed, the compound having the structure: ##STR6## is shown to be useful in said U.S. Pat. No. 3,564,091 issued on Feb. 16, 1971 and the preparation of this compound is set forth at column 4, lines 35-48 of U.S. Pat. No. 3,564,091 the specification for which is incorporated by reference herein.
This compound is also shown to be useful in the perfumery art in copending application for U.S. Pat. Ser. No. 073,289 filed on July 14, 1987 the specification for which is incorporated by reference herein.
The use as a precursor of the genus defined according to the structure: ##STR7## wherein A is an aryl hydrocarbon group of 5-14 carbon atoms and R is an aliphatic hydrocarbon group of more than one carbon atom and the compound: ##STR8## may be phenylethyl alcohol is set forth at lines 40-52, at column 1 of U.S. Pat. No. 3,564,091, to wit:
"More particularly, this invention relates to the use of biocides, compounds selected from the group consisting of (1) esters of boric acid and an alcohol of the formula A--R--OH, wherein A is an aryl hydrocarbon group of 5-14 carbon atoms and R is an aliphatic hydrocarbon group of more than one carbon atom, and (2) A--R--OH alcohol esters of glycol orthoborates wherein A and R are as described above. PA1 In the general formula above, A is preferably selected from the group consisting of phenyl, naphthyl, phenanthracyl, and anthracyl. The glycol is selected from the group consisting of alpha and beta glycols containing 3-20 carbon atoms. The term boric acid embraces ortho-, meta-, and pyroboric acids, and boric oxide." PA1 "wherein each R represents the same or different member of the group consisting of hydrogen and monovalent hydrocarbon radicals including alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups, and R' represents a monovalent hydrocarbon radical including alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups"). PA1 "3,4,5,6,6-PENTAMETHYL HEXANOL-2- AND ALKYL HOMOLOGUES THEREOF; PROCESS FOR PREPARING SAME AND ORGANOLEPTIC USES THEREOF"
U.S. Pat. No. 2,839,564 issued on June 17, 1958; U.S. Pat. No. 2,940,839 issued on June 14, 1960; and U.S. Pat. No. 3,189,637 issued on June 15, 1965 as well as United Kingdom Patent Specification No. 722,538 published on Jan. 26, 1955 each disclose borate esters having the generic structure: ##STR9## wherein R.sub.11, R.sub.12, R.sub.13 and R.sub.14 can represent hydrogen or alkyl and R.sub.15 represent various hydrocarbon moieties (for example the definition of the R moieties at column 1, lines 29-34 of U.S. Pat. No. 2,839,564 states:
The borate esters having the generic structure: ##STR10## as disclosed in the aforementioned Patents and U.K. Patent Specificaton are indicated to be useful in causing fuel to be made more efficient on operation of internal combustion engines by reduction of octane requirements.
The prior art does not set forth explicitedly or implicitedly the use of such a genus or members of such a genus in perfumery or in perfumed articles or perfumed polymers.
U.S. Pat. No. 4,391,999 issued on July 5, 1983 entitled:
on which I am the inventor, discloses the compound having the structure: ##STR11## as being useful in augmenting or enhancing the aroma of perfume compositions and perfumed articles.
The publication "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I, by Steffen Arctander (1969) discloses the usefulness of the compounds having the structure: ##STR12## in augmenting or enhancing the aroma of perfume compositions at, inter alia, Monographs 1427 and 669.
Nothing in the prior art discloses the beta-alkylidene phenethyl alcohol esters and ethers of our invention defined according to the generic structure: ##STR13## wherein R.sub.5 represents hydrogen or methyl; wherein R.sub.6 represents one of the moieties: ##STR14## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents the same or different hydrogen or methyl; wherein R.sub.7 represents methyl or ethyl; and wherein R.sub.8 represents hydrogen or methyl particularly as being useful in augmenting or enhancing the aroma of perfume compositions, perfumed articles and perfumed polymers.